Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(III)/lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin- 3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III),U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UVabsorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO2 2+) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III)complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III)from Ln(III) by quadridentate N-donor ligands.

Association mapping of partitioning loci in barley

Background: Association mapping, initially developed in human disease genetics, is now being applied to plant species. The model species Arabidopsis provided some of the first examples of association mapping in plants, identifying previously cloned flowering time genes, despite high population sub-structure. More recently, association genetics has been applied to barley, where breeding activity has resulted in a high degree of population sub-structure. A major genotypic division within barley is that between winter- and spring-sown varieties, which differ in their requirement for vernalization to promote subsequent flowering. To date, all attempts to validate association genetics in barley by identifying major flowering time loci that control vernalization requirement (VRN-H1 and VRN-H2) have failed. Here, we validate the use of association genetics in barley by identifying VRN-H1 and VRN-H2, despite their prominent role in determining population sub-structure. Results: By taking barley as a typical inbreeding crop, and seasonal growth habit as a major partitioning phenotype, we develop an association mapping approach which successfully identifies VRN-H1 and VRN-H2, the underlying loci largely responsible for this agronomic division. We find a combination of Structured Association followed by Genomic Control to correct for population structure and inflation of the test statistic, resolved significant associations only with VRN-H1 and the VRN-H2 candidate genes, as well as two genes closely linked to VRN-H1 (HvCSFs1 and HvPHYC). Conclusion: We show that, after employing appropriate statistical methods to correct for population sub-structure, the genome-wide partitioning effect of allelic status at VRN-H1 and VRN-H2 does not result in the high levels of spurious association expected to occur in highly structured samples. Furthermore, we demonstrate that both VRN-H1 and the candidate VRN-H2 genes can be identified using association mapping. Discrimination between intragenic VRN-H1 markers was achieved, indicating that candidate causative polymorphisms may be discerned and prioritised within a larger set of positive associations. This proof of concept study demonstrates the feasibility of association mapping in barley, even within highly structured populations. A major advantage of this method is that it does not require large numbers of genome-wide markers, and is therefore suitable for fine mapping and candidate gene evaluation, especially in species for which large numbers of genetic markers are either unavailable or too costly.

BTBPs versus BTPhens: some reasons for their differences in properties concerning the partitioning of minor actinides and the advantages of BTPhens

Two members of the tetradentate N-donor ligand families 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO−LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO−LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol−1) energy barrier to rotation about the central biaryl C−C axis in order to achieve the cis−cis conformation that is required to form a complex, whereas the cis−cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10- coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.

Graph-based algorithms for comparison and prediction of household-level energy use profiles

We present an efficient graph-based algorithm for quantifying the similarity of household-level energy use profiles, using a notion of similarity that allows for small time–shifts when comparing profiles. Experimental results on a real smart meter data set demonstrate that in cases of practical interest our technique is far faster than the existing method for computing the same similarity measure. Having a fast algorithm for measuring profile similarity improves the efficiency of tasks such as clustering of customers and cross-validation of forecasting methods using historical data. Furthermore, we apply a generalisation of our algorithm to produce substantially better household-level energy use forecasts from historical smart meter data.

Characterization of energy flux partitioning in urban environments: links with surface seasonal properties

A better understanding of links between the properties of the urban environment and the exchange to the atmosphere is central to a wide range of applications. The numerous measurements of surface energy balance data in urban areas enable intercomparison of observed fluxes from distinct environments. This study analyzes a large database in two new ways. First, instead of normalizing fluxes using net all-wave radiation only the incoming radiative fluxes are used, to remove the surface attributes from the denominator. Second, because data are now available year-round, indices are developed to characterize the fraction of the surface (built; vegetation) actively engaged in energy exchanges. These account for shading patterns within city streets and seasonal changes in vegetation phenology; their impact on the partitioning of the incoming radiation is analyzed. Data from 19 sites in North America, Europe, Africa, and Asia (including 6-yr-long observation campaigns) are used to derive generalized surface–flux relations. The midday-period outgoing radiative fraction decreases with an increasing total active surface index, the stored energy fraction increases with an active built index, and the latent heat fraction increases with an active vegetated index. Parameterizations of these energy exchange ratios as a function of the surface indices [i.e., the Flux Ratio–Active Index Surface Exchange (FRAISE) scheme] are developed. These are used to define four urban zones that characterize energy partitioning on the basis of their active surface indices. An independent evaluation of FRAISE, using three additional sites from the Basel Urban Boundary Layer Experiment (BUBBLE), yields accurate predictions of the midday flux partitioning at each location.

Utilizing electronic effects in the modulation of BTPhen ligands with respect to the partitioning of minor actinides from lanthanides

Effects of bromine substitution at the 5 and 5,6-positions of the 1,10-phenanthroline nucleus of BTPhen ligand on their extraction properties for Ln(III) andAn(III) cations have been studied. Compared to C5-BTPhen, electronic modulation in BrC5-BTPhen and Br2C5-BTPhen enabled these ligands to be fine-tuned in order to enhance the separation selectivity of Am(III) from Eu(III)

Mg/Ca partitioning between aqueous solution and aragonite mineral: a molecular dynamics study

We have calculated the concentrations of Mg in the bulk and surfaces of aragonite CaCO3 in equilibrium with aqueous solution, based on molecular dynamics simulations and grand-canonical statistical mechanics. Mg is incorporated in the surfaces, in particular in the (001) terraces, rather than in the bulk of aragonite particles. However, the total Mg content in the bulk and surface of aragonite particles was found to be too small to account for the measured Mg/Ca ratios in corals. We therefore argue that most Mg in corals is either highly metastable in the aragonite lattice, or is located outside the aragonite phase of the coral skeleton, and we discuss the implications of this finding for Mg/Ca paleothermometry.

Improved evaporative flux partitioning and carbon flux in the land surface model JULES: impact on the simulation of land surface processes in temperate Europe

The primary role of land surface models embedded in climate models is to partition surface available energy into upwards, radiative, sensible and latent heat fluxes. Partitioning of evapotranspiration, ET, is of fundamental importance: as a major component of the total surface latent heat flux, ET affects the simulated surface water balance, and related energy balance, and consequently the feedbacks with the atmosphere. In this context it is also crucial to credibly represent the CO2 exchange between ecosystems and their environment. In this study, JULES, the land surface model used in UK weather and climate models, has been evaluated for temperate Europe. Compared to eddy covariance flux measurements, the CO2 uptake by the ecosystem is underestimated and the ET overestimated. In addition, the contribution to ET from soil and intercepted water evaporation far outweighs the contribution of plant transpiration. To alleviate these biases, adaptations have been implemented in JULES, based on key literature references. These adaptations have improved the simulation of the spatio-temporal variability of the fluxes and the accuracy of the simulated GPP and ET, including its partitioning. This resulted in a shift of the seasonal soil moisture cycle. These adaptations are expected to increase the fidelity of climate simulations over Europe. Finally, the extreme summer of 2003 was used as evaluation benchmark for the use of the model in climate change studies. The improved model captures the impact of the 2003 drought on the carbon assimilation and the water use efficiency of the plants. It, however, underestimates the 2003 GPP anomalies. The simulations showed that a reduction of evaporation from the interception and soil reservoirs, albeit not of transpiration, largely explained the good correlation between the carbon and the water fluxes anomalies that was observed during 2003. This demonstrates the importance of being able to discriminate the response of individual component of the ET flux to environmental forcing.

High resolution simulation of the variability of surface energy balance fluxes across central London with urban zones for energy partitioning

The parameterization of surface heat-flux variability in urban areas relies on adequate representation of surface characteristics. Given the horizontal resolutions (e.g. ≈0.1–1km) currently used in numerical weather prediction (NWP) models, properties of the urban surface (e.g. vegetated/built surfaces, street-canyon geometries) often have large spatial variability. Here, a new approach based on Urban Zones to characterize Energy partitioning (UZE) is tested within a NWP model (Weather Research and Forecasting model;WRF v3.2.1) for Greater London. The urban land-surface scheme is the Noah/Single-Layer Urban Canopy Model (SLUCM). Detailed surface information (horizontal resolution 1 km)in central London shows that the UZE offers better characterization of surface properties and their variability compared to default WRF-SLUCM input parameters. In situ observations of the surface energy fluxes and near-surface meteorological variables are used to select the radiation and turbulence parameterization schemes and to evaluate the land-surface scheme

Multilevel research in the field of organizational behavior: an empirical look at 10 years of theory and research

During the last 30 years, significant debate has taken place regarding multilevel research. However, the extent to which multilevel research is overtly practiced remains to be examined. This article analyzes 10 years of organizational research within a multilevel framework (from 2001 to 2011). The goals of this article are (a) to understand what has been done, during this decade, in the field of organizational multilevel research and (b) to suggest new arenas of research for the next decade. A total of 132 articles were selected for analysis through ISI Web of Knowledge. Through a broad-based literature review, results suggest that there is equilibrium between the amount of empirical and conceptual papers regarding multilevel research, with most studies addressing the cross-level dynamics between teams and individuals. In addition, this study also found that the time still has little presence in organizational multilevel research. Implications, limitations, and future directions are addressed in the end. Organizations are made of interacting layers. That is, between layers (such as divisions, departments, teams, and individuals) there is often some degree of interdependence that leads to bottom-up and top-down influence mechanisms. Teams and organizations are contexts for the development of individual cognitions, attitudes, and behaviors (top-down effects; Kozlowski & Klein, 2000). Conversely, individual cognitions, attitudes, and behaviors can also influence the functioning and outcomes of teams and organizations (bottom-up effects; Arrow, McGrath, & Berdahl, 2000). One example is when the rewards system of one organization may influence employees’ intention to quit and the existence or absence of extra role behaviors. At the same time, many studies have showed the importance of bottom-up emergent processes that yield higher level phenomena (Bashshur, Hernández, & González-Romá, 2011; Katz-Navon & Erez, 2005; Marques-Quinteiro, Curral, Passos, & Lewis, in press). For example, the affectivity of individual employees may influence their team’s interactions and outcomes (Costa, Passos, & Bakker, 2012). Several authors agree that organizations must be understood as multilevel systems, meaning that adopting a multilevel perspective is fundamental to understand real-world phenomena (Kozlowski & Klein, 2000). However, whether this agreement is reflected in practicing multilevel research seems to be less clear. In fact, how much is known about the quantity and quality of multilevel research done in the last decade? The aim of this study is to compare what has been proposed theoretically, concerning the importance of multilevel research, with what has really been empirically studied and published. First, this article outlines a review of the multilevel theory, followed by what has been theoretically “put forward” by researchers. Second, this article presents what has really been “practiced” based on the results of a review of multilevel studies published from 2001 to 2011 in business and management journals. Finally, some barriers and challenges to true multilevel research are suggested. This study contributes to multilevel research as it describes the last 10 years of research. It quantitatively depicts the type of articles being written, and where we can find the majority of the publications on empirical and conceptual work related to multilevel thinking.

Exogenous alpha-Synuclein decreases raft partitioning of Cav2.2 channels inducing dopamine release

alpha-Synuclein is thought to regulate neurotransmitter release through multiple interactions with presynaptic proteins, cytoskeletal elements, ion channels, and synaptic vesicles membrane. alpha-Synuclein is abundant in the presynaptic compartment, and its release from neurons and glia has been described as responsible for spreading of alpha-synuclein-derived pathology. alpha-Synuclein-dependent dysregulation of neurotransmitter release might occur via its action on surface-exposed calcium channels. Here, we provide electrophysiological and biochemical evidence to show that alpha-synuclein, applied to rat neurons in culture or striatal slices, selectively activates Cav2.2 channels, and said activation correlates with increased neurotransmitter release. Furthermore, in vivo perfusion of alpha-synuclein into the striatum also leads to acute dopamine release. We further demonstrate that alpha-synuclein reduces the amount of plasma membrane cholesterol and alters the partitioning of Cav2.2 channels, which move from raft to cholesterol-poor areas of the plasma membrane. We provide evidence for a novel mechanism through which alpha-synuclein acts from the extracellular milieu to modulate neurotransmitter release and propose a unifying hypothesis for the mechanism of alpha-synuclein action on multiple targets: the reorganization of plasma membrane microdomains.

Foreign executive appointments: a multilevel examination

As multinational enterprises (MNE) expand, their attachment to the country of origin is challenged by the need to adapt to an increasingly diverse geographical posture. We examine how these countervailing forces affect top management team (TMT) composition and test a model that associates foreign executive appointments with individual- and firm-level antecedents. Using multilevel data comprising 1,446 TMT appointments at 360 large European firms between 2001 and 2005, we show that individual experiential characteristics, the type of TMT function, prior performance of the MNE, and the MNE’s overall degree of internationalization are associated with foreign TMT appointments. We discuss how our findings contribute to the international business literature and complement recent research on the internationalization of TMTs.

An isotope dilution model for partitioning phenylalanine and tyrosine uptake by the mammary gland of lactating dairy cows

An isotope dilution model for partitioning phenylalanine and tyrosine uptake by the mammary gland of the lactating dairy cow is constructed and solved in the steady state. The model contains four intracellular and four extracellular pools and conservation of mass principles are applied to generate the fundamental equations describing the behaviour of the system. The experimental measurements required for model solution are milk secretion and plasma flow rate across the gland in combination with phenylalanine and tyrosine concentrations and plateau isotopic enrichments in arterial and venous plasma and free and protein bound milk during a constant infusion of [1-(13)C]phenylalanine and [2,3,5,6-(2)H]tyrosine tracer. If assumptions are made, model solution enables determination of steady state flows for phenylalanine and tyrosine inflow to the gland, outflow from it and bypass, and flows representing the synthesis and degradation of constitutive protein and hydroxylation. The model is effective in providing information about the fates of phenylalanine and tyrosine in the mammary gland and could be used as part of a more complex system describing amino acid metabolism in the whole ruminant.

Software evolution: a graph based model

A model based on graph isomorphisms is used to formalize software evolution. Step by step we narrow the search space by an informed selection of the attributes based on the current state-of-the-art in software engineering and generate a seed solution. We then traverse the resulting space using graph isomorphisms and other set operations over the vertex sets. The new solutions will preserve the desired attributes. The goal of defining an isomorphism based search mechanism is to construct predictors of evolution that can facilitate the automation of ’software factory’ paradigm. The model allows for automation via software tools implementing the concepts.

The effect of alkyl substitution on the extraction properties of BTPhen ligands for the partitioning of trivalent minor actinides and lanthanides in spent nuclear fuels

Bis-triazinylphenanthroline ligands (BTPhens), which contain additional alkyl (n-butyl and sec-butyl) groups attached to the triazine rings, have been synthesized, and the effects of this alkyl substitution on their extraction properties with Ln(III) and An(III) cations in simulated nuclear waste solutions have been studied. The speciation of n-butyl-substituted ligand (C4- BTPhen) with some trivalent lanthanide nitrates was elucidated by 1 H-NMR spectroscopic titrations. These experiments have shown that the dominant species in solution were the 1:2 complexes [Ln(III)(BTPhen)2], even at higher Ln(III) concentrations, and the relative stability of 2:1 to 1:1 BTPhen-Ln(III) complexes varied with different lanthanides. As expected, sec-butylsubstituted ligand (sec-C4 BTPhen) showed higher solubility than C4-BTPhen in certain diluents. A greater separation factor (SFAm/Eu = ca. 210) was observed for sec-C4-BTPhen compared to C4-BTPhen (SFAm/Eu = ca. 125) in 1-octanol at 4 M HNO3 solutions. The greater separation factor may be due to the higher solubility of the 2:1 complex for sec-C4-BTPhen at the interface than the 1:1 complex of C4-BTPhen.